Category

Published on

08 Jul 2008

Abstract

The solution of the Schrödinger equation (wave equations) for the hydrogen atom uses the fact that the Coulomb potential produced by the nucleus is isotropic (it is radially symmetric in space and only depends on the distance to the nucleus). Although the resulting energy eigenfunctions (the "orbitals") are not necessarily isotropic themselves, their dependence on the angular coordinates follows completely generally from this isotropy of the underlying potential: The eigenstates of the Hamiltonian (= energy eigenstates) can be chosen as simultaneous eigenstates of the angular momentum operator. This corresponds to the fact that angular momentum is conserved in the orbital motion of the electron around the nucleus. Therefore, the energy eigenstates may be classified by two angular momentum quantum numbers, l and m (integer numbers). The "angular momentum" quantum number l = 0, 1, 2, ... determines the magnitude of the angular momentum. The "magnetic" quantum number m = −l, .., +l determines the projection of the angular momentum on the (arbitrarily chosen) z-axis.

In addition to mathematical expressions for total angular momentum and angular momentum projection of wavefunctions, an expression for the radial dependence of the wave functions must be found. It is only here that the details of the 1/r Coulomb potential enter (leading to Laguerre polynomials in r). This leads to a third quantum number, the principal quantum number n = 1, 2, 3, ... The principal quantum number in hydrogen is related to atom's total energy.

Note that the maximum value of the angular momentum quantum number is limited by the principal quantum number: it can run only up to n − 1, i.e. l = 0, 1, ..., n − 1.

Due to angular momentum conservation, states of the same l but different m have the same energy (this holds for all problems with rotational symmetry). In addition, for the hydrogen atom, states of the same n but different l are also degenerate (i.e. they have the same energy). However, this is a specific property of hydrogen and is no longer true for more complicated atoms which have a (effective) potential differing from the form 1/r (due to the presence of the inner electrons shielding the nucleus potential).

Taking into account the spin of the electron adds a last quantum number, the projection of the electron's spin angular momentum along the z axis, which can take on two values. Therefore, any eigenstate of the electron in the hydrogen atom is described fully by four quantum numbers. According to the usual rules of quantum mechanics, the actual state of the electron may be any superposition of these states. This explains also why the choice of z-axis for the directional quantization of the angular momentum vector is immaterial: An orbital of given l and m' obtained for another preferred axis z' can always be represented as a suitable superposition of the various states of different m (but same l) that have been obtained for z.